Manufacture of asphalt



H. R. ROSENBAUM.

MANUFACTURE 0F ASPHALT.

APPLICATION man APR.2,1915. RENEwED JULY 29,1918.

Patented Maf.

m m m I :RUDOLPH R. ROSENIBUM, OF CHICAGO, LLINOIS, ASSIGNOR T0 CENTRAL COMMERCIAL COMPANY, OF CHICAGO, ILLINOIS, A GRPOLRATION 0F ILLINOIS.

iunnunac'rnnn or assistanat Lacasse.

Specification of vLetters Patent.

Patenten naar. a.' ieee.

Application filed April 2,1915, Serial No. 18,857. Renewed July 29, 1918. Serial No. tlt. l

To all whom t may concern:

Be it known that l, RUDOLPH R. ROSEN- BAUM, a subject of the Emperor of Germany, and resident of Chicago, county of Cook, and State of lllinois, have invented certain new7 and useful Improvements in the Manufacture'of Asphalt, of which the following is a specification. i

The invention relates to a process of treating solid mineral bitumens for producing materials of improved quality andi having a wider range of commercial utility and to' asphalt which may be produced by the said process. Some of the solid mineral b-itumens, more particularly the asphaltites, or so-called as haltic coals, are wholly nonmeltable whi e others are only imperfectly meltable. That is to say, `theminerals referred to are subject either to a complete or to a partial destructive distillation by heat before a melting temperature is reached.

A mineral of the kind described oceurs`in considerable quantity at Sardis, near Tuskahema, lPushmataha county, Oklahoma, and is now commerciall from earthy substances. Some samples are soluble to the extent of ninety-seven per cent. of their weight in carbon bisulfid and contain scarcely one per cent. of inorganic mineral matter. In its original condition, however, the mineral is a black, hard, but riable substance, scarcely distinguishable in appearance from anthracite coal. 0n being heated, it decomposet without the slightest evidence of meltingfand is readily inflammable. Similar asphaltites occur in other localities, for exam-ple, albertite.

The non-meltable or imperfectly meltable character of these asphaltites renders thein quite unfit in their natural state for many of the con'nnercial uses to which the meltable solid bitumens have been applied. The present invention accordingly contemplates a process by which'the non-meltable and imperfectly meltable asphaltites are transformed into perfectly nieltable products having increased commercial value and the said products. The object of the invention is to provide a simple and inexpensive process for accomplishing this result.

ln the accompanying drawings- Figure 1 is a central sectional View partly in elevation, showing a form of apparatus known as grahamite. This mineralis obtainable substantially free in which the improved process maybe carried out, and

Figs. 2 and 3 are transverse sectional views taken on the lines 2-2 and 3 3 respectively, of Fig. l. y

The meltable asphalts, as, for example,

natural uintahite- (gilsonite), are perfectly soluble in carbon tetrachlorid and are trequently regarded as consisting of a mixture of two compounds, or groups of compounds, known, respectively, as asphaltene and petrolene. -l)etrolene is distinguished from asphaltene through the fact that petrolene is soluble in naphtha while asphaltene is not'.

rlhe grahamite heretofore mentioned, on the other hand, is soluble only to the extent of about fifteen per cent. of its weight in carbon tetrachlorid, and to the extent of less than lone per cent. of its weight in naphtha. It is accordingly substantially devoid' of the so-called petrolene constituents of the meltteA able asphalts, like uintahite, and is also 'to a y follows that the'bitumens of which the natu-r`r ral mineral is principally-composed are profoundly modified. in character.

In carrying out the process a quantity of the selected asphaltite is continuously subjected to heat and pressure for a prolonged period. The desired conditions are conveniently obtained by heating the material in a closed retort as 10, the pressure resulting from the generation and connement of gas. ln the event that a wholly non-Ineltahle asphaltite is used, a small proportion of flux is dsirably added. lf the flux employed contain paraffin hydrocarbons, the gas for providing the pressure comprises methane, supplied by the cracking of lthe paraiiin hydrocarbons, this cracking of the parain hydrocarbons also resulting in the formation of a black solid hydrocarbon which becomes associated with the mass and is a constituent of the finished product.

For the purpose of demonstrating that this is so, ll have carefully prepared a small quantity of a pure solid paran hydrocarbon shown by combustion analysis to have the formula CZSHES. For this purpose l eX- tracted a commercial paraiiirscale having a melting point of 124.-A degrees Fahrenheit, with a light gasolene and precipitated the paraffin hydrocarbon from this solution with acetic ether, the extraction of the precipitate with a light gasolene and the reprecipitation of the parain from `the solution being repeated until the crystalline character of the precipitate, observed with a microscope, showed the precipitate to be a pure product. This product was cracked byheat producing a gas and a black solid hydrocarbon soluble in carbon tetrachlorid, but not soluble in naphtha. A combustion analysis of the black solid hydrocarbon showed-it to have the composition CNH, and a Hempel analysis of the gas showed it to consist principally of methane. lt theretore follows that the cracking of the paraflin hydrocarbon @28H58 is substantially repe resented by the equation- Furthermore in the commercial practice of the invention l preferably provide the retort l() with a gas outlet 17 to which a laterally opening pet cock 18 is applied to permit of the removal of samples oi" the gas.

A Hempel analysis of samples of gas drawn p from this pet cock showsthat the gas consists principally of methane.

rlhev commercial practice of the process does not require the selection of a pure paraiiin as the source of the parailin hydrocarbon. lt is suggested that any material capable of being cracked by heat into an inert gas and a residue miscible with the modified bitumens will serve as a fluir when any is required. inasmuch as the resulting product is a meltable asphalt, a mixture ot paraiiinhydrocarbons and asphalte, as in the residuum from a mixed base petroleum, may be employed. llhe asphalte occurring in the residuum from the mixed base petroleums are in no wise objectionable, but are simply retained as constituents of the finished product. ln treating1 the grahamite heretofore mentioned, a residuum from mixed base (lllinois) petroleum, of the grade commercially lrnownl `as 12o-14 Baume flux oil, has been found to yield satisfactory results. Analysis has shown that this residuum contains from two to four lper cent. of solid paraffin.

A continued application of heat and pressure alone suiices for the production of ay meltable product. 'The reaction is expedited, however, and the resulting product greatly improved if a reducing agent be provided as by the liberation of nascent hydrogen in the heated batch. rFhis liberation of nascent hydrogen has been conveniently ac- Lacasse complished by the reaction of caustic soda upon iron, 1n accordance with the equation `of the l2o to 14:0 Baume iuX oil fromA lllinois petroleum, and one per cent. by weight retort and subjected to a temperature of 400 Fahrenheit and a. resulting pressureot ifty pounds per square inch for a period of twenty-four hours, produces a lustrous black solid asphalt melting at 380o Fahrenheit, perfectly soluble in carbon bisulfid and carbon tetrachlorid and soluble to the extent ot'y forty-three per cent. of its weight in naphtha. lThis product, while having a conchoidal fracture and otherwise resembling a natural uintahite (gilsonite), is distinguished therefrom by having a higher melting point and by being pure black in powdered form, but more particularly by containinga larger proportion of constituents soluble inl naphtha and by being more viscous wlien first melted. Preferably the selected quantity of petroleum,.residuum is irst introduced into the retort l0 and heated alone to a temperature of 250o Fahrenheit. rlhe illing opening 1l of the retort mayv be left open during this part of the process, it desired. rlhe full quantity of grahamite in lump form and the caustic soda is then added and the filling opening 11 sealed with a man-hole cover 12. The heating of the retort is accomplished by the maintenance or' a suitable fire in the furnace i3. As' shown, this furnace is constructed with .return lues 21, 22, one extending'along each side of the retort l0. These return lines lead to a stack (not shown), through downcoiners 23, 24, and a smoke tunnel 25. Preterably the retort 10, is provided with a pressure gage 14e and with a depending tube 15, closed at its lower end, for the introduction of a thermometer (not shown), to permit observations of the pressure and teniperature to be made from time to time. ln order that the desired pressure maybe attained but not exceeded the gas outlet pipe 17 is provided with an automatic pressure regulating valve-19 which may be adjusted to permit the How of gas through the pipe only when the desired pressure.,- as 50 lbs., per square inch, is reached. llt is also ad- 'of dry caustic soda, ii'lield in a closed iron il l5 ,melting point is desired.

lessees visable to provide the-retort 10 with safety valves 16, two of which are shown, as a pre caution against a dangerous rise in pressure in event the gas is produced with too great rapidity to pass od through the outlet pipe 17. l prefer to adjust the safety valves 16 to open at a pressure which exceeds that at which the pressure regulating valve 19 opens byabout two pounds per square inch. The completed product is most 'conveniently withdrawn from the retort while still soft, as through an outlet pipe 26 controlled by a valve 27. This pipe is preferably protected from direct exposure to the heat of the fire, as by being inclosed with masonry walls 28.

A comparison of the original grahamite and the result-ing product, obtained by the use of the process in the` specific manner herein described, is conveniently shown by' the following table:

lt will be observed that the portion soluble in naphtha is increased .by an amount greater than the entire addition of petroleum residuum, and that a considerable portion of bitumen originally insoluble in parbon tetrachlorid has been so modified as o 'be completely extracted by this solvent. As a further evidence oi the modification of the original constituents it is found that the product is entirely free from parailin.

rllhe character of the resulting product may be varied by the use oi' diderent relative proportions of Hux and the selected asphaltite, a larger proportion of flux being employed when a product having a lower Modifications in the character of the product may also be made by varvinathe temperature, the pressure, or the length of time during which the materials are subjected to treatment. These modifications of the process permit the manufacture ot' products having melting points which vary trom 150O l11 arhenheit to 4200 lFahrenheit. ln so tar as these products are comparablej as to their melting points. with natural uintahite, the portion ot the product soluble in naphtha is in each case greater than in the natural uint-aliite melting at the same temperature. The temperature towhich'the mixed. materials are .subjected preferably about 200 llahrenheit abo re the melting point desired tor the finished product, as naphthas ot dililerent specific gravity and -lfrom diiierent sources behare differently as solvents of asphalt constituents, it is noted that the naphtha herein referred to is of Baume tromv llllinois crude petroleum and is used as a solvent at the room temperature. i

lclaim as my inventionl. The improved process of treating nonmeltable or impertectly meltable bitumen to render it meltable., which consists in'subjecting the same to the simultaneous action of heat anda Huid .pressure of substantial intensity above that of the atmosphere and continuing the treatment until a homogeneous melted product is obtained.

2. The improved process of treating nonmeltable or impertectly meltableV bitumen to render it meltable, -which consists in mixing the same with a quantity of paraffin hydrocarbon and subjecting the mixture to the action of heat in a retort constructed for the coniinement ot the generated gas at high pressure., and continuing the treatment until a homogeneous melted product is obtained.

3. The improved process ottreating nonmeltable or imperfectly meltable bitumen to render it meltable, which consists in mixing the same with a quantity of paraiiin hydrocarbon and an alkali and exposing the mixture to ametal and to the action of heat in a retort constructed for the confinement of the generated gas at high pressure and continuing the treatment until a homogeneousJmelted product is obtained.

4. The improved process of treating nonmeltable or imperfectly meltable bitumen to render it meltable, which consists in subjecting the same to the simultaneous action of heat vand pressure and to that ot nascent hydrogen, and continuing the treatment until a homogeneous melted product is obtained.

5. The improved method of manufacturing a meltable asphalt which consists in subj ecting a mixture ot a mixed base petroleum residuuin and an asphaltic coal to the application ot heat in a retort constructed tor the confinement of the generated gas at liigli,p1'essure and continuing the treatment until' a homogeneous melted product is obtained.

6. The improved method oit 1nanui`acturing a meltable asphalt which consists in subjecting a mixture of a mixed base petroleum residuum and an asphalt'ic coal with agents tor the production ot nascent hydrogen to the application of heat in a retort constructed for the confinement ot the generated gas at high pressure, and continuing the treatment until a homogeneous melted product is obtained.

7. The improved method of manufacturing a meltable asphalt which consists in subj eeting` a mixture of a mixed base petroleum residuum, an asphaltic coal, and an alkali 'to the application of heat in an iron retort constructed tor the connnement et the generated at high, pressure and .continuing lll@ meltable bitumen and an agent from which gas is evolved When heated, While the said the treatment until a .homogeneous melted product is obtained.

8. The improved method of manufacturing a meltable asphalt which consists of the application of heat to a non-meltable Abitumen in the presence of gas While the said materials are held in a retort which is constructed for the confinement of the gas at high pressure, and continuing the treatment until a homogeneous melted product is obtained. Y

9. The improved method ofmanufacturing a meltable asphalt which consists of the application of heat to a non-meltable bitumen "in the presence of an inert gas and agents for the production of nascent hydrogen while the said materials are held in a retort which is constructed for the confinement of the gas at high pressure 'and continuing the treatment until a homogeneous melted product is obtained.

1Q-'Phe improved method of treating a non-meltable bitumen to produce meltable asphalt which consists in subjecting the same to the action of heat in the presence of agents'which are cracked by heat to produce a gas and a residue which is'miscible with the bitumen While the. said materials are held in a retort which is constructed for the confinement of the gas at high pressure, and continuing the treatment until a homogene- Ious melted product is obtained.

11. The improved process of treating nonmeltable or imperfectly meltable bitumento produce a meltable asphalt lWhich consists in subjecting the same to the. simultane-l ous action of heat, pressure and a reducing agent and continuing the treatment until a homogeneous melted product is obtained.

l2. rPhe improved method of manufacturing a meltable asphalt which consists of the application of heat to a. non-meltable bitumen in the presencel of gas and a reducing agent While the said materials are held in a retort Which is constructed for the confinement of the gas at high ressure and con- .tinuing the treatment until a homogeneous melted product is obtained.

13. lPhe improved method of manufacturing meltable asphalt, `Which consists of the application of heat to a mixture of a nonmaterials are heldin a retort Which is constructed for the confinement of the gas at high pressure, and continuing the treatment until a homogeneous melted product is obtained.

14:. rlhe improved method of manufacturing meltable asphalt Which consists of the application of heat to a material comprising a non-meltable bitumen and from which gas is evolved When heated While the said material is held in a retort which is constructed for the confinement of the gas at high pres- Laagste 16. Prepared meltable asphalt characterized by substantially complete solubility in carbon tetrachlorid and by comprising a greater proportion of petrolene than is found in natural uintalite melting at a temperature which is not higher than the melting point of the said prepared asphalt.

17. Prepared asphalt melting at 380 derees Fahrenheit and comprising asphaltene fty-six per cent. and petrolene forty-three per cent.

18. Prepared asphalt solid at ordinary temperatures but meltable without decomposition, of lustrous black appearance, conchoidal fracture and possessing the characteristics of a' product obtained by prolonged exposure of a natural non-meltable asphaltite to heat and pressure.

19. Prepared asphalt solid at ordinary temperatures 'but meltable Without decomposition, of lustrous black appearance, conchoidal fracture,'and possessing the characteristics of a product obtained. by prolonged exposure of a natural non-meltable asphaltite to heat and pressure with agents for the production of nascent hydrogen.

20. Prepared asphalt comprising petrolene Which etrolene is of a black color and lsolid at ordinary temperatures.

hydrogen in a closed retort.

.123. Prepared asphalt solid atj' ordinary temperatures but meltable without decom* position, of lustrous black appearance, conchoidal fracture, and possessing the characteristics of a product obtained by prolonged heating of a mixture of a natural nonmeltable asphaltite, petroleum residuum, and an alkali in a closed iron retort.

24. Prepared asphalt comprising petro- Maase@ lene which petrolene s solid at ordinary temperatures.

25. Prepared asphalt free from para'ln.

26. Prepared asphalt comprising petro- 5 lene which petrolene is of a black color.

27, Prepared asphalt comprising asphaltene which asphaltene s of a blaokcolor, solid at ordinary temperatures but melting at 2280 F. and contains carbon and hydrogen lo in proportions represented by the formula 28. Prepared asphalt comprising asphaltene which asphaltene s of the character resulting from the cracking of pax-ao by pr longed exposure to heat and a luiol pressure of substantial intensity' above that of the atmosphere.

RUDOLPH R RSENBAUM.

Witnessesz CHARLES B. GrLLsoN, E. M. KLATCIER. 

